catena-Poly[[μ-bromido-(μ-hydroxydi-2-pyridylmethano­lato-κ4N,O:O,N′)dicopper(II)(Cu—Cu)]-di-μ-bromido]

Zeller, M.; Westcott, B.L.; Kopp-Vaughn, K.M.; Hunter, A.D.

doi:10.1107/S1600536808024197

metal-organic compounds

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Volume 64| Part 9| September 2008| Page m1121

doi:10.1107/S1600536808024197

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catena-Poly[[μ-bromido-(μ-hydroxydi-2-pyridylmethanolato-κ⁴N,O:O,N′)dicopper(II)(Cu—Cu)]-di-μ-bromido]

Matthias Zeller,^a Barry L. Westcott,^b ^* Kristin M. Kopp-Vaughn ^b and Allen D. Hunter ^a

^aDepartment of Chemistry, Youngstown State University, Youngstown, OH 44555, USA, and ^bDepartment of Chemistry and Biochemistry, Central Connecticut State University, New Britain, CT 06050, USA
^*Correspondence e-mail: westcottb@ccsu.edu

(Received 19 June 2008; accepted 29 July 2008; online 6 August 2008)

The title complex, [Cu₂Br₃(C₁₁H₉N₂O₂)]_n, was one of three isolated by slow evaporation of an acetonitrile reaction mixture of CuBr₂ with di-2-pyridyl ketone (1:1 molar ratio). The title complex contains a 2:1 metal-to-ligand ratio of copper(II) with the hydrated form of the ligand, di-2-pyridylmethanediol. The two copper centers are bridged by a bromide ion and the alkoxy O atom, and the Cu—Cu distance is 2.9801 (5) Å. The dimeric units are further linked by bromide ions, leading to a two-dimensional extended bridged structure. O—H⋯O hydrogen bonds are present in the crystal structure.

Related literature

Apart from the title complex, two others were isolated from the reaction mixture and structurally characterized. One was identical to that of Parker et al. (2000 ), the other is reported in the following paper by Westcott et al. (2008 ). For other related structures, see: Wang et al. (1986 ); Mariezcurrena et al. (1999 ).

Experimental

Crystal data

[Cu₂Br₃(C₁₁H₉N₂O₂)]
M_r = 568.01
Triclinic, $[P \overline 1]$
a = 8.7708 (7) Å
b = 9.6018 (8) Å
c = 10.1839 (8) Å
α = 73.7060 (10)°
β = 70.8520 (10)°
γ = 63.9280 (10)°
V = 718.28 (10) Å³
Z = 2
Mo Kα radiation
μ = 11.30 mm⁻¹
T = 100 (2) K
0.39 × 0.19 × 0.08 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003 ) T_min = 0.122, T_max = 0.424
7397 measured reflections
3537 independent reflections
3305 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.061
S = 1.09
3537 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 1.02 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.84	2.33	3.014 (2)	139
Symmetry code: (i) -x, -y+2, -z+1.

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808024197/fj2131sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024197/fj2131Isup2.hkl

checkCIF report

Comment top

The structure of the title compound, is shown below. The complex was one of three Cu-dpkoh complexes isolated from the 1:1 molar mixture of copper(II)bromide and di-2-pyridyl ketone. The title complex was the second isolated from solution. One other complex had been reported previously by Parker, et al., another unique complex is described elsewhere: Westcott, et al.(2008).

The complex contains two copper centers that are 2.9801 (5) Å apart and are bridged by the hydrated form of the ligand di-2-pyridylketone. Each copper center is also coordinated to the ligand through one unique nitrogen atom and a by a µ-hydroxyl bridge. Additionally, each Cu center coordinates one bromide ion. The bromide ion then acts as a bridging ligand to the next di-copper unit, leading to a polymeric structure as shown in Figure 2.

Related literature top

Apart from the title complex, two others were isolated from the reaction mixture and structurally characterized. One was identical to that of Parker et al. (2000), the other is reported by Westcott, et al. (2008). For other related structures, see: Wang et al. (1986); Mariezcurrena et al. (1999).

Experimental top

Di-2-pyridyl ketone (dpk) was purchased from Aldrich and used as received. Copper(II) bromide hexahydrate was dried in an oven at 110 C for 48 h before use. DPK (1 mmol) and copper(II) bromide (1 mmol) were combined in 40 ml of acetonitirle and stirred for 30 minutes. The resulting green crystals were isolated after 4 days by slow evaporation of the solution.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP-3 (Farrugia, 1997) representation of the asymmetric unit. Ellipsoids are drawn at the 30% probability level.
	Fig. 2. Packing diagram showing the extended structure.

catena-Poly[[µ-bromido-(µ-hydroxydi-2-pyridylmethanolato- κ⁴N,O:O,N')dicopper(II)(Cu—Cu)]-di-µ-bromido] top

Crystal data top

[Cu₂Br₃(C₁₁H₉N₂O₂)]	Z = 2
M_r = 568.01	F(000) = 536
Triclinic, P1	D_x = 2.626 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.7708 (7) Å	Cell parameters from 6753 reflections
b = 9.6018 (8) Å	θ = 2.4–30.6°
c = 10.1839 (8) Å	µ = 11.30 mm⁻¹
α = 73.706 (1)°	T = 100 K
β = 70.852 (1)°	Hexagon, green
γ = 63.928 (1)°	0.39 × 0.19 × 0.08 mm
V = 718.28 (10) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	3537 independent reflections
Radiation source: fine-focus sealed tube	3305 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 28.3°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003)	h = −11→11
T_min = 0.122, T_max = 0.424	k = −12→12
7397 measured reflections	l = −13→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0301P)² + 0.561P] where P = (F_o² + 2F_c²)/3
3537 reflections	(Δ/σ)_max = 0.002
182 parameters	Δρ_max = 1.02 e Å⁻³
0 restraints	Δρ_min = −0.61 e Å⁻³

Crystal data top

[Cu₂Br₃(C₁₁H₉N₂O₂)]	γ = 63.928 (1)°
M_r = 568.01	V = 718.28 (10) Å³
Triclinic, P1	Z = 2
a = 8.7708 (7) Å	Mo Kα radiation
b = 9.6018 (8) Å	µ = 11.30 mm⁻¹
c = 10.1839 (8) Å	T = 100 K
α = 73.706 (1)°	0.39 × 0.19 × 0.08 mm
β = 70.852 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	3537 independent reflections
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003)	3305 reflections with I > 2σ(I)
T_min = 0.122, T_max = 0.424	R_int = 0.021
7397 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.061	H-atom parameters constrained
S = 1.09	Δρ_max = 1.02 e Å⁻³
3537 reflections	Δρ_min = −0.61 e Å⁻³
182 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br2	0.12154 (3)	1.22298 (3)	0.70734 (3)	0.01693 (7)
Br3	−0.23030 (3)	1.19011 (3)	1.00202 (3)	0.01823 (7)
Br1	0.57965 (3)	0.99477 (3)	0.65263 (3)	0.01507 (7)
Cu1	0.32811 (4)	0.96542 (3)	0.64120 (3)	0.01335 (8)
Cu2	−0.03366 (4)	1.04405 (4)	0.82256 (3)	0.01406 (8)
O2	0.1101 (2)	0.9459 (2)	0.65750 (18)	0.0130 (3)
O1	0.1005 (2)	0.7855 (2)	0.53023 (19)	0.0181 (4)
H1	0.0027	0.8513	0.5168	0.027*
N1	0.4203 (3)	0.7340 (2)	0.6562 (2)	0.0142 (4)
C6	0.1192 (3)	0.7966 (3)	0.6588 (3)	0.0136 (5)
N2	−0.1178 (3)	0.8719 (3)	0.8672 (2)	0.0148 (4)
C7	−0.0283 (3)	0.7649 (3)	0.7798 (3)	0.0146 (5)
C5	0.3027 (3)	0.6743 (3)	0.6683 (2)	0.0132 (5)
C4	0.3512 (3)	0.5141 (3)	0.6783 (3)	0.0165 (5)
H4	0.2670	0.4726	0.6880	0.020*
C3	0.5248 (3)	0.4151 (3)	0.6739 (3)	0.0181 (5)
H3	0.5603	0.3051	0.6801	0.022*
C11	−0.2540 (3)	0.8573 (3)	0.9709 (3)	0.0194 (5)
H11	−0.3182	0.9345	1.0310	0.023*
C1	0.5880 (3)	0.6375 (3)	0.6519 (3)	0.0181 (5)
H1A	0.6702	0.6812	0.6426	0.022*
C10	−0.3034 (4)	0.7321 (4)	0.9924 (3)	0.0231 (6)
H10	−0.3998	0.7232	1.0667	0.028*
C9	−0.2103 (4)	0.6209 (3)	0.9042 (3)	0.0250 (6)
H9	−0.2400	0.5328	0.9187	0.030*
C2	0.6449 (3)	0.4767 (3)	0.6606 (3)	0.0185 (5)
H2	0.7641	0.4106	0.6575	0.022*
C8	−0.0737 (4)	0.6390 (3)	0.7948 (3)	0.0213 (5)
H8	−0.0116	0.5661	0.7305	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br2	0.01628 (12)	0.01244 (12)	0.02349 (13)	−0.00619 (10)	−0.00358 (10)	−0.00520 (10)
Br3	0.01571 (12)	0.01965 (14)	0.01898 (13)	−0.00469 (10)	−0.00213 (9)	−0.00841 (10)
Br1	0.01576 (12)	0.01633 (13)	0.01651 (12)	−0.00878 (10)	−0.00493 (9)	−0.00191 (9)
Cu1	0.01234 (14)	0.01089 (15)	0.01833 (16)	−0.00526 (12)	−0.00342 (11)	−0.00347 (12)
Cu2	0.01375 (15)	0.01408 (15)	0.01601 (15)	−0.00656 (12)	−0.00140 (11)	−0.00535 (12)
O2	0.0129 (8)	0.0090 (8)	0.0178 (8)	−0.0051 (6)	−0.0021 (6)	−0.0038 (6)
O1	0.0200 (9)	0.0172 (9)	0.0191 (9)	−0.0040 (7)	−0.0094 (7)	−0.0055 (7)
N1	0.0152 (10)	0.0135 (10)	0.0149 (10)	−0.0050 (8)	−0.0044 (8)	−0.0034 (8)
C6	0.0159 (11)	0.0111 (11)	0.0162 (11)	−0.0057 (9)	−0.0054 (9)	−0.0028 (9)
N2	0.0146 (10)	0.0163 (10)	0.0153 (10)	−0.0068 (8)	−0.0055 (8)	−0.0014 (8)
C7	0.0130 (11)	0.0138 (12)	0.0191 (12)	−0.0063 (9)	−0.0062 (9)	−0.0010 (9)
C5	0.0155 (11)	0.0130 (12)	0.0110 (10)	−0.0056 (9)	−0.0027 (9)	−0.0023 (9)
C4	0.0181 (12)	0.0144 (12)	0.0177 (12)	−0.0074 (10)	−0.0028 (9)	−0.0033 (9)
C3	0.0222 (13)	0.0105 (11)	0.0174 (12)	−0.0041 (10)	−0.0036 (10)	−0.0010 (9)
C11	0.0174 (12)	0.0253 (14)	0.0162 (12)	−0.0098 (11)	−0.0051 (10)	−0.0005 (10)
C1	0.0168 (12)	0.0207 (13)	0.0186 (12)	−0.0064 (10)	−0.0045 (9)	−0.0065 (10)
C10	0.0208 (13)	0.0283 (15)	0.0228 (13)	−0.0165 (12)	−0.0082 (10)	0.0074 (11)
C9	0.0230 (14)	0.0217 (14)	0.0346 (16)	−0.0151 (12)	−0.0106 (12)	0.0044 (12)
C2	0.0170 (12)	0.0158 (12)	0.0205 (13)	−0.0021 (10)	−0.0057 (10)	−0.0051 (10)
C8	0.0191 (12)	0.0146 (12)	0.0329 (15)	−0.0085 (10)	−0.0083 (11)	−0.0021 (11)

Geometric parameters (Å, º) top

Br2—Cu1	2.4592 (4)	N2—C11	1.341 (3)
Br2—Cu2	2.4613 (4)	N2—C7	1.346 (3)
Br3—Cu2	2.3507 (4)	C7—C8	1.386 (4)
Br1—Cu1	2.3862 (4)	C5—C4	1.387 (3)
Br1—Cu1ⁱ	2.7923 (4)	C4—C3	1.389 (4)
Cu1—O2	1.9513 (17)	C4—H4	0.9500
Cu1—N1	1.981 (2)	C3—C2	1.374 (4)
Cu1—Br1ⁱ	2.7923 (4)	C3—H3	0.9500
Cu1—Cu2	2.9801 (5)	C11—C10	1.389 (4)
Cu2—O2	1.9386 (17)	C11—H11	0.9500
Cu2—N2	1.979 (2)	C1—C2	1.384 (4)
O2—C6	1.396 (3)	C1—H1A	0.9500
O1—C6	1.410 (3)	C10—C9	1.380 (4)
O1—H1	0.8400	C10—H10	0.9500
N1—C1	1.344 (3)	C9—C8	1.381 (4)
N1—C5	1.344 (3)	C9—H9	0.9500
C6—C5	1.535 (3)	C2—H2	0.9500
C6—C7	1.542 (3)	C8—H8	0.9500

Cu1—Br2—Cu2	74.551 (13)	O2—C6—C7	108.55 (19)
Cu1—Br1—Cu1ⁱ	87.045 (12)	O1—C6—C7	109.37 (19)
O2—Cu1—N1	82.07 (8)	C5—C6—C7	113.9 (2)
O2—Cu1—Br1	172.49 (5)	C11—N2—C7	119.6 (2)
N1—Cu1—Br1	99.71 (6)	C11—N2—Cu2	126.15 (19)
O2—Cu1—Br2	81.11 (5)	C7—N2—Cu2	114.21 (17)
N1—Cu1—Br2	155.54 (6)	N2—C7—C8	121.3 (2)
Br1—Cu1—Br2	94.848 (14)	N2—C7—C6	115.8 (2)
O2—Cu1—Br1ⁱ	94.28 (5)	C8—C7—C6	122.8 (2)
N1—Cu1—Br1ⁱ	91.84 (6)	N1—C5—C4	121.0 (2)
Br1—Cu1—Br1ⁱ	92.955 (12)	N1—C5—C6	115.0 (2)
Br2—Cu1—Br1ⁱ	107.004 (14)	C4—C5—C6	123.9 (2)
O2—Cu1—Cu2	39.84 (5)	C5—C4—C3	119.0 (2)
N1—Cu1—Cu2	103.54 (6)	C5—C4—H4	120.5
Br1—Cu1—Cu2	132.975 (15)	C3—C4—H4	120.5
Br2—Cu1—Cu2	52.757 (10)	C2—C3—C4	119.8 (2)
Br1ⁱ—Cu1—Cu2	126.084 (13)	C2—C3—H3	120.1
O2—Cu2—N2	82.40 (8)	C4—C3—H3	120.1
O2—Cu2—Br3	172.22 (6)	N2—C11—C10	121.6 (3)
N2—Cu2—Br3	99.71 (6)	N2—C11—H11	119.2
O2—Cu2—Br2	81.30 (5)	C10—C11—H11	119.2
N2—Cu2—Br2	163.70 (6)	N1—C1—C2	122.2 (2)
Br3—Cu2—Br2	96.420 (15)	N1—C1—H1A	118.9
O2—Cu2—Cu1	40.15 (5)	C2—C1—H1A	118.9
N2—Cu2—Cu1	113.10 (6)	C9—C10—C11	119.0 (3)
Br3—Cu2—Cu1	142.336 (15)	C9—C10—H10	120.5
Br2—Cu2—Cu1	52.692 (10)	C11—C10—H10	120.5
C6—O2—Cu2	117.17 (15)	C10—C9—C8	119.3 (3)
C6—O2—Cu1	117.19 (14)	C10—C9—H9	120.3
Cu2—O2—Cu1	100.01 (8)	C8—C9—H9	120.3
C6—O1—H1	109.5	C3—C2—C1	118.3 (2)
C1—N1—C5	119.6 (2)	C3—C2—H2	120.8
C1—N1—Cu1	124.95 (18)	C1—C2—H2	120.8
C5—N1—Cu1	115.39 (17)	C9—C8—C7	119.2 (3)
O2—C6—O1	111.3 (2)	C9—C8—H8	120.4
O2—C6—C5	109.75 (19)	C7—C8—H8	120.4
O1—C6—C5	104.04 (19)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱⁱ	0.84	2.33	3.014 (2)	139

Symmetry code: (ii) −x, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu₂Br₃(C₁₁H₉N₂O₂)]
M_r	568.01
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.7708 (7), 9.6018 (8), 10.1839 (8)
α, β, γ (°)	73.706 (1), 70.852 (1), 63.928 (1)
V (Å³)	718.28 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	11.30
Crystal size (mm)	0.39 × 0.19 × 0.08

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS in SAINT-Plus; Bruker, 2003)
T_min, T_max	0.122, 0.424
No. of measured, independent and observed [I > 2σ(I)] reflections	7397, 3537, 3305
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.061, 1.09
No. of reflections	3537
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.02, −0.61

Computer programs: SMART (Bruker, 2002), SAINT-Plus (Bruker, 2003), SHELXTL (Sheldrick, 2008) and ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.84	2.33	3.014 (2)	139

Symmetry code: (i) −x, −y+2, −z+1.

Acknowledgements

The authors thank Dr Guy Crundwell (CCSU) for helpful discussions. BLW acknowledges funding from the National Science Foundation (NSF # 0420322). MZ and ADH acknowledge funding from the National Science Foundation (NSF #0087210) and the Ohio Board of Regents (CAP-491).

References

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